JP5644405B2 - toner - Google Patents

Description

  The present invention relates to a toner obtained by heterogeneous polymerization of a ring-opening polymerizable monomer in a compressive fluid.

Methods for producing fine polymer particles by heterogeneous polymerization of monomers in supercritical carbon dioxide are well known and include emulsion polymerization, dispersion polymerization and suspension polymerization.
Heterogeneous polymerization in supercritical carbon dioxide has the following advantages compared to heterogeneous polymerization in water and organic solvents, so it is used in a method for producing fine polymer particles from various monomers. The obtained polymer particles are used in various applications such as electrophotographic developers, printing inks, architectural paints, and cosmetics.
(1) The solvent removal after polymerization and the drying process can be simplified.
(2) Waste solvent treatment is unnecessary.
(3) It is not necessary to use a highly toxic organic solvent.
(4) The remaining unreacted monomer components and harmful substances can be removed by the washing step.
(5) The carbon dioxide used can be recovered and reused.

For example, Patent Document 1 discloses a method of synthesizing colored polymer particles from a radical polymerizable monomer in the presence of a surfactant containing a perfluoroalkyl group. However, the fluorosurfactant used in this method is very expensive and has a problem in terms of safety. In addition, polymer particles having a small molecular weight distribution (Mw / Mn) (about 2 or less) cannot be obtained.
Further, Patent Document 2 uses a polymer radical polymerization initiator having an organosiloxane skeleton, and simultaneously synthesizes a polymer surfactant in one pot without separately preparing and preparing a surfactant according to the monomer. A method for obtaining polymer particles is disclosed. However, this method cannot obtain a polymer particle having a molecular weight distribution (Mw / Mn) of 2 or less. Moreover, there is no description regarding a ring-opening polymerizable monomer.
Therefore, a method for producing polymer particles having a small molecular weight distribution using a ring-opening polymerizable monomer in a compressive fluid such as a supercritical fluid is not known.

  By the way, petroleum-derived thermoplastic resins such as styrene / acrylic resins and polyester resins are used as binder resins used for toners. However, in recent years, due to environmental considerations, attention has been focused on methods that use biomass-derived biodegradable resins made from renewable resources as binder resins for toners, which have little impact on the environment when discarded. A method has been proposed.

  As one means for this, there is an example of using a biodegradable microorganism-produced aliphatic polyester as a binder resin (for example, Patent Documents 3 and 4). When the polyester is used as a toner resin, Since the softening temperature is high, the fixing temperature must be set high, which is not suitable from the viewpoint of energy saving. As a technique for lowering the fixing temperature, a method of lowering the softening temperature by adding a large amount of plant-based wax to the biodegradable resin (for example, Patent Document 5) has been proposed, but the softening temperature of the toner is lowered. Even if this is possible, the toner tends to aggregate due to the wax component, and problems such as poor productivity and poor toner transportability due to poor toner fluidity occur.

In order to obtain low-temperature fixability and fixing stability, a method using two types of resins having different softening points and a binder resin containing a biodegradable resin (for example, Patent Documents 6 and 7) has also been proposed. . In these methods, a resin having a low softening point serves as a bridge between a resin having a high softening point and a biodegradable resin, and the biodegradable resin is uniformly dispersed in the binder resin. However, if the blending ratio of the biodegradable resin is set high, the biodegradable resin may be poorly dispersed, resulting in a decrease in developability due to variations in charging performance, and the durability deteriorates. The compounding ratio in the resin is as low as about 20% by mass.
Furthermore, although not clearly specified in any of the prior arts, the systems using these biodegradable resins are reduced in glass transition point and heat distortion temperature due to moisture absorption, and are transported and stored under high temperature and high humidity. In this case, the particles or the formed image are stuck, and there is a disadvantage that it cannot be used.

  As described above, there are many problems to make the biodegradable resin as the main resin component of the binder resin of the toner, and in order to achieve both heat and heat storage resistance and low-temperature fixability, Further improvements in physical properties are needed.

  An object of the present invention is to provide a toner having a small molecular weight distribution and excellent in low-temperature fixability, wet heat storage resistance, and environmental stability. It is another object of the present invention to provide a toner that can obtain the same effect even when a biodegradable resin is used as a main resin component of the binder resin of the toner.

The above problems are solved by the following inventions (1) to (12).
(1) A toner obtained by granulation while polymerizing a ring-opening polymerizable monomer using a catalyst in the presence of a surfactant and a colorant in a compressive fluid.
(2) The toner according to (1), wherein the catalyst is an organic catalyst.
(3) The toner according to (2), wherein the organic catalyst is a basic nucleophilic nitrogen compound.
(4) The toner according to (2) or (3), wherein the organic catalyst is a cyclic compound containing a nitrogen atom.
(5) The organic catalyst is selected from a cyclic amine, a cyclic diamine, a cyclic diamine compound having an amidine skeleton, a cyclic triamine compound having a guanidine skeleton, a heterocyclic aromatic organic compound containing a nitrogen atom, and an N-heterocyclic carbene. The toner according to any one of (2) to (4) above, wherein the toner is one of the above.
(6) The organic catalyst is 1,4-diazabicyclo- [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5. , 7-triazabicyclo [4.4.0] dec-5-ene (TBD), diphenylguanidine (DPG), N, N-dimethyl-4-aminopyridine (DMAP), 4-pyrrolidinopyridine (PPY) The toner according to (5) above, which is any one of 1,3-di-tert-butylimidazol-2-ylidene (ITBU).
(7) The toner according to any one of (1) to (6), wherein the colorant is a pigment.
(8) The toner according to any one of (1) to (7), wherein the ring-opening polymerizable monomer is L- or D-lactic acid lactide.
(9) The toner according to any one of (1) to (8) above, wherein the surfactant has affinity for both the compressive fluid and the ring-opening polymerizable monomer.
(10) The toner according to any one of (1) to (9), wherein the surfactant has any one of a perfluoroalkyl group, a polydimethylsiloxane group, and a polyacrylate group.
( 11 ) The toner according to any one of (1) to ( 10 ) above, wherein the toner has a molecular weight distribution (Mw / Mn) of 1.5 or less. However, Mw represents a mass average molecular weight and Mn represents a number average molecular weight.
(12) A method for producing a toner, comprising granulating a compressive fluid while polymerizing a ring-opening polymerizable monomer using a catalyst in the presence of a surfactant and a colorant.

  According to the present invention, it is possible to provide a toner having a small molecular weight distribution and excellent in low-temperature fixability, wet heat and heat storage stability, and environmental stability. Also, a toner having the same effect can be provided by using a biodegradable resin as a main resin component of the binder resin of the toner.

The phase diagram for demonstrating a compressible fluid. The figure for demonstrating the area | region by the kind of compressible fluid. 1 is a schematic configuration diagram of a main part of an image forming apparatus (copier) used in an embodiment.

Hereinafter, the present invention will be described in detail.
The present invention is characterized in that the polymerization of the ring-opening polymerizable monomer and the granulation (granulation) of the produced polymer are performed at once in a compressive fluid. The present invention is the first granulation of a polymer using a ring-opening polymerizable monomer in a compressive fluid.

(Compressible fluid)
In the present invention, the term “compressible fluid” means that a substance exists in any of the regions (1), (2), and (3) shown in FIG. 2 in the phase diagram shown in FIG. Means the state.
In such a region, it is known that the substance has a very high density and behaves differently from that at normal temperature and pressure. In addition, when a substance exists in the area | region of (1), it becomes a supercritical fluid. A supercritical fluid exists as a non-condensable high-density fluid in a temperature and pressure range that exceeds the limit (critical point) at which gas and liquid can coexist, does not cause condensation even when compressed, is above the critical temperature and is critical A fluid in a state of pressure or higher. Further, when the substance is present in the region (2), it becomes a liquid, but in the present invention, it is obtained by compressing a substance that is in a gaseous state at normal temperature (25 ° C.) and normal pressure (1 atm). Represents liquefied gas. Further, when the substance is present in the region (3), it is in a gaseous state, but in the present invention, it represents a high pressure gas having a pressure of 1/2 Pc or more.

Examples of substances that can be used in the state of a compressive fluid include carbon monoxide, carbon dioxide, dinitrogen monoxide, nitrogen, methane, ethane, propane, 2,3-dimethylbutane, and ethylene. These may be used alone or in combination of two or more.
Among these, carbon dioxide is preferable in that it has a critical pressure of about 7.4 MPa and a critical temperature of about 31 ° C., can easily create a supercritical state, and is nonflammable and easy to handle.
In view of increasing the efficiency of the reaction, for example, when the compressive fluid is carbon dioxide, the temperature is preferably 25 ° C. or higher, and the higher the pressure, the higher the solubility of the surfactant.

(Ring-opening polymerizable monomer)
The ring-opening polymerizable monomer that can be polymerized in the present invention is not particularly limited as long as it has an ester bond in the ring, and examples thereof include cyclic esters and cyclic carbonates.
As the cyclic ester, known ones can be used without particular limitation, and as a particularly preferable monomer, a cyclic ester obtained by dehydration condensation of the L-form or D-form of the compound represented by the following general formula (A) A dimer is mentioned.

（Ｒは炭素数１〜１０のアルキル基を表す）

(R represents an alkyl group having 1 to 10 carbon atoms)

  Specific examples of the compound represented by the general formula (A) include enantiomers of lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid. Isomers, 2-hydroxyheptanoic acid enantiomer, 2-hydroxyoctanoic acid enantiomer, 2-hydroxynonanoic acid enantiomer, 2-hydroxydecanoic acid enantiomer, 2-hydroxyundecanoic acid mirror image Isomers, enantiomers of 2-hydroxydodecanoic acid and the like. Among these, enantiomers of lactic acid are particularly preferable from the viewpoint of reactivity and availability. These cyclic dimers can be used alone or in admixture of several kinds.

Examples of cyclic esters other than the above general formula (A) include β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, and δ-hexalano. Examples thereof include aliphatic lactones such as lactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, β-methyl-δ-valerolactone, glycolide, and lactide. In particular, ε-caprolactone is preferable from the viewpoint of reactivity and availability.
Examples of the cyclic carbonate include, but are not limited to, ethylene carbonate and propylene carbonate.
The ring-opening polymerizable monomer can be used alone or in combination of several kinds, but the glass transition point of the obtained polymer is preferably room temperature or higher. If the glass transition point is too low, it may not be extracted as particles.

(catalyst)
In the polymerization of the ring-opening polymerizable monomer, either a metal catalyst or an organic catalyst not containing a metal atom can be used, but an organic catalyst is preferable in consideration of the influence on the environment. Any organic catalyst may be used as long as it contributes to the ring-opening reaction of the ring-opening polymerizable monomer, forms an active intermediate with the ring-opening polymerizable monomer, and is desorbed and regenerated by reaction with alcohol. Although the polymerization reaction proceeds even with a cationic catalyst, hydrogen is extracted from the polymer main chain (back-biting), the molecular weight distribution is widened, and it is difficult to obtain a high molecular weight nitrogen compound. Is preferred. More preferably, it is a cyclic compound containing a nitrogen atom. Examples of such compounds include cyclic amines, cyclic diamines (cyclic diamine compounds having an amidine skeleton), cyclic triamine compounds having a guanidine skeleton, heterocyclic aromatic organic compounds containing a nitrogen atom, and N-heterocyclic carbene. Etc.
Examples of the metal catalyst include derivatives of zinc, lead, titanium, bismuth, zirconium, germanium, cobalt, and the like. Examples of the derivative include metal organic compounds, carbonates, oxides, halides, and the like.

  Examples of cyclic amines are quinuclidine, and examples of cyclic diamines are 1,4-diazabicyclo- [2.2.2] octane (DABCO), 1,5-diazabicyclo (4,3,0) nonene-5]. Examples of cyclic diamine compounds having an amidine skeleton include 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), diazabicyclononene; examples of cyclic triamine compounds having a guanidine skeleton; 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), diphenylguanidine (DPG); examples of heterocyclic aromatic organic compounds containing nitrogen atoms include N N-dimethyl-4-aminopyridine (DMAP), 4-pyrrolidinopyridine (PPY), pyrocholine, imidazole, pyrimidine, purine; N-hete Examples of cyclic carbenes, 1,3-di -tert- butyl-2-ylidene (ITBU) but the like, but is not limited thereto. Of these, DABCO, DBU, DPG, TBD, DMAP, PPY, and ITBU are preferable.

  The type and amount of the organic catalyst varies depending on the combination of the compressive fluid and the ring-opening polymerizable monomer, and thus cannot be specified unconditionally, but is preferably 0.01 to 15 mol% with respect to 100 mol% of the ring-opening polymerizable monomer. More preferably, it is 0.1-1 mol%, More preferably, it is 0.3-0.5 mol%. If the amount used is less than 0.01 mol%, the organic catalyst may be deactivated before the polymerization reaction is completed, and a polymer having a target molecular weight may not be obtained. On the other hand, when the amount used exceeds 15 mol%, it may be difficult to control the polymerization reaction.

  The polymerization reaction temperature also varies depending on the combination of the compressive fluid, the ring-opening polymerizable monomer, and the organic catalyst, and thus cannot be generally specified. However, in normal cases, the polymerization reaction temperature is about 40 to 150 ° C., preferably 50 to 120 degreeC, More preferably, you may be 60-100 degreeC. If it is less than 40 degreeC, reaction rate will fall easily and a polymerization reaction may not be able to advance quantitatively. Further, if the temperature exceeds 150 ° C., the depolymerization reaction also occurs in equilibrium, so that the polymerization reaction is difficult to proceed quantitatively.

The polymerization reaction time may be appropriately set according to the target molecular weight. If the molecular weight is in the range of 3,000 to 100,000, it is usually 2 to 12 hours. In order to increase the polymerization rate, a polymerization time of 5 to 72 hours is required, but the polymerization is stopped in a desired particle size and particle size distribution state, a polymerization initiator is sequentially added, The polymerization rate can be increased by carrying out the reaction.
Further, in order to proceed the polymerization reaction uniformly and quantitatively, the density difference may be compensated by stirring so that the polymer particles do not settle due to the density difference from the monomer.
The pressure at the time of polymerization, that is, the pressure of the compressive fluid is not a problem even in a liquefied gas or a high-pressure gas state. A pressure at which a supercritical state is obtained is preferable. When the compressed fluid is carbon dioxide, it is 3.7 MPa or more, preferably 7.4 MPa or more.

(Polymerization initiator)
In the polymerization, it is preferable to add a ring-opening polymerization initiator in order to control the molecular weight of the resulting polymer. As the ring-opening polymerization initiator, known ones can be used, and any alcohol-based mono-, di- or polyhydric alcohols may be used, and either saturated or unsaturated may be used. Absent.
Specifically, monoalcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol; ethylene glycol, 1,2-propanediol (Propylene glycol), 1,3-propanediol, 1,3-butanediol, 1,4-butanediol (tetramethylene glycol), 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol , Neopentyl glycol, hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, nonanediol, polyethylene glycol, hydrogenated hydrogen Dialcohols such as dihydric alcohols obtained by adding cyclic ethers such as ethylene oxide and propylene oxide to phenol A and bisphenol A; polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, erythritol, triethanolamine; and Examples include methyl lactate and ethyl lactate. It is also possible to synthesize diblock and triblock copolymers by using a polymer having an alcohol residue at the terminal.

What is necessary is just to adjust suitably the usage-amount of a ring-opening polymerization initiator according to the target molecular weight, and about 0.1-5 mass parts is preferable with respect to 100 mass parts of ring-opening polymerizable monomers.
If necessary, a polymerization terminator (benzoic acid, hydrochloric acid, phosphoric acid, metaphosphoric acid, acetic acid, lactic acid, etc.) can be used after the polymerization reaction.

(Surfactant)
In the present invention, a surfactant that dissolves in the compressive fluid and has an affinity for both the compressive fluid and the ring-opening polymerizable monomer coexists in the polymerization system. For example, when supercritical carbon dioxide is used as the compressive fluid, a surfactant having a parent CO ₂ group and a parent monomer group in the molecule is used. Examples of the parent CO ₂ group in this case include a perfluoroalkyl group, a polydimethylsiloxane group, a polyacrylate group, an ether group, and a carbonyl group. The parent monomer group can be selected according to the type of monomer used. For example, when lactide or lactone is used as the monomer, an activator having a carbonyl group such as an ester bond or an amide bond is preferred. .
When the surfactant is allowed to coexist in the polymerization system, it may be added to the compressive fluid or to the ring-opening polymerizable monomer.

  Specific examples of the surfactant include those having any of the following general formulas (1) to (7) as a partial structure.

（式（１）中、Ｒ１〜Ｒ５は水素原子又は炭素数１〜４の低級アルキル基、Ｒ６〜Ｒ８は炭素数１〜４の低級アルキル基を表す。また、ｍ、ｎ及びｋは繰り返し単位を表す整数であり、ｍ／ｎ＝０．３〜７０、１≦ｋ≦４を満たす。界面活性剤の分子量は７０００以下である。）

(In Formula (1), R1-R5 represents a hydrogen atom or a C1-C4 lower alkyl group, R6-R8 represents a C1-C4 lower alkyl group. Moreover, m, n, and k are repeating units. And m / n = 0.3 to 70, satisfying 1 ≦ k ≦ 4. The molecular weight of the surfactant is 7000 or less.)

（式（２）中、Ｒ９は水素原子又はメチル基、Ｒ１０はメチレン基又はエチレン基、Ｒｆは炭素数が７〜１０のパーフルオロアルキル基を表す。また、ｑは繰り返し単位を表す整数である。界面活性剤の分子量は２５００以下である。）

(In formula (2), R9 represents a hydrogen atom or a methyl group, R10 represents a methylene group or an ethylene group, Rf represents a perfluoroalkyl group having 7 to 10 carbon atoms, and q represents an integer representing a repeating unit. The molecular weight of the surfactant is 2500 or less.)

（式（３）中、Ｒ９は、水素原子又はメチル基を表す。また、ｒ及びｐは繰り返し単位を表す整数である。界面活性剤の分子量は５５００以下である。）

(In Formula (3), R9 represents a hydrogen atom or a methyl group. R and p are integers representing a repeating unit. The molecular weight of the surfactant is 5500 or less.)

（式（４）中、Ｒ６〜Ｒ８およびＲは炭素数１〜４の低級アルキル基を表す。また、ｍ、ｎ及びｐは繰り返し単位を表す整数であり、ｍ／ｎ＝０．３〜７０を満たす。界面活性剤の分子量は５０００以下である。

(In Formula (4), R6-R8 and R represent a C1-C4 lower alkyl group. Moreover, m, n, and p are integers representing a repeating unit, and m / n = 0.3-70. The molecular weight of the surfactant is 5000 or less.

（式（５）中、ｎは繰り返し単位を表す整数である。界面活性剤の分子量は５０００以下である。

(In formula (5), n is an integer representing a repeating unit. The molecular weight of the surfactant is 5000 or less.

（式（６）中、Ｒ９は炭素数１〜４の低級アルキル基を表す。また、ｍ、ｎは繰り返し単位を表す整数であり、ｍ／ｎ＝０．３〜７０を満たす。界面活性剤の分子量は５０００以下である。

(In formula (6), R9 represents a lower alkyl group having 1 to 4 carbon atoms, and m and n are integers representing repeating units, and satisfy m / n = 0.3 to 70.) Has a molecular weight of 5000 or less.

（式（７）中、Ｒ１０は炭素数１〜４の低級アルキル基を表し、Ｘは酸素原子又は硫黄原子を表す。また、ｍ、ｎは繰り返し単位を表す整数であり、ｍ／ｎ＝０．３〜７０を満たす。界面活性剤の分子量は５０００以下である。

(In formula (7), R10 represents a lower alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and m and n are integers representing a repeating unit, and m / n = 0. 3 to 70. The molecular weight of the surfactant is 5000 or less.

Among these, the surfactant represented by the formula (1) is particularly preferable. R6 to R8 are preferably methyl groups, and k is preferably 2. When k is small, the pyrrolidone skeleton and the silicone skeleton are close to each other in three dimensions, so that the function as a surfactant is lowered. Moreover, when k becomes large, the solubility in a compressible fluid may fall.
Among the surfactants represented by the above formula (1), the following [Surfactant 1] is particularly preferable. The surfactant represented by [Surfactant 1] is sold under the trade name of “Monacil PCA” by Croda Japan Co., Ltd.

[Surfactant 1]

  The surfactant used in the present invention is represented by the general formulas (1) to (7) as long as it is soluble in the compressive fluid and has an affinity for both the compressive fluid and the ring-opening polymerizable monomer. It can be used with anything other than the same. For example, what has a structure shown by the following general formula (8)-(11) is mentioned.

（上記一般式（８）〜（１１）中、ｍ、ｎは繰り返し単位を表す整数である。）

(In the general formulas (8) to (11), m and n are integers representing repeating units.)

The surfactant is appropriately selected depending on the type of compressive fluid to be used, the production of polymer particles and seed particles (described later) or the production of grown particles, and in particular in the sense of sterically preventing coalescence of the polymer particles. Those having high affinity and adsorbability to the polymer particle surface and high affinity to compressible fluid and high solubility are preferred.
Further, in order to enhance the repulsion between particles in a three-dimensional manner, a molecular chain having a certain length, preferably a molecular weight of 10,000 or more is selected. However, if the molecular weight is too large, the liquid viscosity is remarkably increased, the operability and the stirring property are deteriorated, and the precipitation probability of the produced polymer on the particle surface varies.

  The amount of the surfactant used varies depending on the kind of the ring-opening polymerizable monomer and the kind of the surfactant, but is usually 0.1 to 10% by mass with respect to the compressive fluid, and more preferably 1 ˜5 mass%. When the concentration of the surfactant is low, the generated polymer particles have a relatively large particle size, and when the concentration is high, the particle size becomes small. Less effective.

Particles generated in the early stage of polymerization are stabilized by a surfactant present while maintaining an equilibrium between the compressive fluid and the surface of the polymer particles, but when a large amount of ring-opening polymerizable monomer is present in the compressive fluid, Since the polymer particle concentration becomes high, the steric repulsion force of the surfactant is overcome and agglomerates. Further, when the amount of the ring-opening polymerizable monomer is extremely large with respect to the compressive fluid, the produced polymer is completely dissolved and does not precipitate unless the polymerization proceeds to some extent. The state of precipitation in this case takes the form of forming a highly sticky lump.
Therefore, the amount of the ring-opening polymerizable monomer with respect to the compressive fluid when producing the polymer particles is naturally limited, and the density varies depending on the state of the compressive fluid, but varies slightly, but is approximately 500% by mass or less. The amount is preferably 250% by mass or less.

-Polymerization method-
In a compressive fluid, in the presence of a surfactant and a colorant, granulation is carried out while polymerizing a ring-opening polymerizable monomer using a catalyst, whereby polymer particles having an average particle size in the range of submicron to 1 mm (toner) ) Can be obtained. The particle size can be controlled by the pressure, temperature, reaction time, amount of surfactant, etc. during the reaction, and various polymer particles from true spheres to irregular shapes can be obtained by changing the reaction conditions as necessary. Can be obtained.
Examples of the polymerization method include dispersion polymerization, suspension polymerization, and emulsion polymerization, and they can be used properly according to the purpose. In particular, the advantage of using a compressive fluid can be utilized, and dispersion polymerization is superior to suspension polymerization or emulsion polymerization in terms of monodispersibility of polymer particles and narrow distribution of particle diameter.

Alternatively, a method may be used in which polymer particles (seed particles) having a smaller particle size distribution than the target particle size are added in advance, and the monomer is reacted and grown in the same system as described above.
The monomer used for the growth reaction may be the same monomer that produced the seed particles, or another monomer, but the polymer produced should not dissolve in the compressible fluid.
By returning the compressive fluid in which the polymer obtained by the above method is dispersed to normal temperature and pressure, dried polymer particles can be obtained.

For example, after the surfactant is completely dissolved in the compressive fluid, one or more ring-opening polymerizable monomers and a polymerization initiator are added, and the flow in the reaction vessel becomes uniform. What is necessary is just to heat to the temperature corresponding to the decomposition | disassembly rate of a polymerization initiator, stirring at such a speed | rate. In general, the heating temperature is preferably 40 to 100 ° C, particularly preferably 50 to 85 ° C.
Since the temperature at the initial stage of polymerization has a large effect on the particle size of the polymer particles to be produced, the temperature is raised to the polymerization temperature after adding the ring-opening polymerizable monomer, and the initiator is dissolved in a small amount of compressive fluid and added. Is preferable.
In the polymerization, it is necessary to sufficiently expel moisture contained in the air of the reaction vessel with an inert gas such as nitrogen gas, argon gas, oxygen dioxide gas or the like. If moisture removal is insufficient, the particle size cannot be made uniform, and fine particles are likely to be generated.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent used for this invention, According to the objective, it can select suitably from a well-known pigment, The following are illustrated.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. .
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.

Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These can use 1 type (s) or 2 or more types.

  Particularly preferred are Pigment Yellow PY93, PY128, PY155, PY180, PY74, Pigment Blue PB15: 3, Pigment Red PR122, PR269, PR184, PR57: 1, PR238, PR146, PR185, Pigment Blue PB15: 3, and Carbon Black. is there.

  The pigment may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the pigment with high shearing force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the pigment and the resin. The so-called flushing method is also preferable in that the wet cake of the pigment can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing pigment water is mixed or kneaded together with a resin and an organic solvent, and the pigment is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

  The content of the pigment in the colored polymer particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and particularly 3 -10 mass% is preferable. When the content is less than 0.1% by weight, when used as a toner, a reduction in the coloring power of the toner is observed. When the content exceeds 20% by weight, poor dispersion of the pigment in the toner occurs, and the coloring power is reduced. This may lead to a decrease in the electrical characteristics of the toner.

-Preparation method of pigment dispersion-
The pigment dispersion of the present invention comprises at least a mixture of the ring-opening polymerizable monomer and the pigment in the presence of a medium such as glass beads, zirconia beads, alumina beads, iron balls, a side grinder, a paint shoer, a ball milling device, a sand mill. After the pigment is pulverized and uniformly mixed or dissolved in a device, etc., the ring-opening polymerizable monomer composition from which the media has been removed is further introduced into a high-pressure cell containing a supercritical fluid (or subcritical fluid) and stirred. The pigment dispersion used in the present invention containing the pigment, the ring-opening polymerizable monomer, and the supercritical fluid (or subcritical fluid) can be obtained by dispersing and mixing with a sufficient shearing force.

As for the method of mixing and dispersing with supercritical fluid (or subcritical fluid), other methods of introducing supercritical fluid (or subcritical fluid) into ring-opening polymerizable monomer composition, ring-opening polymerizable monomer composition Examples include a method of introducing a liquid into the liquid and heating it to bring the liquid into a supercritical state. Any method can be used as long as it is a method used for the purpose of the present invention.
Further, a pigment may be dispersed in a supercritical fluid (or subcritical fluid), and a ring-opening polymerizable monomer may be added thereto.

  In the composition of the pigment dispersion, the pigment is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the ring-opening polymerizable monomer. is there. If the composition is less than 0.1 part by mass, sufficient coloring power cannot be obtained, and if it exceeds 50 parts by mass, it is not preferable in terms of aggregation, sedimentation, or thickening of the pigment.

In the present invention, a pigment dispersant may be used in combination, and known ones can be used.
Examples of pigment dispersants include basic polymer copolymer dispersants, modified polyurethane dispersants, acidic polymer copolymer dispersants, polyester dispersants, acrylic acid, methacrylic acid and polymers of these esters. And colorant derivatives.
Specific examples of the modified polyurethane-based dispersants include “Ajisper PB711”, “Azisper PB821”, and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.) as the basic polymer copolymer dispersant, and “EFKA- 4060 "," EFKA-4080 "," EFKA-7462 "," EFKA-4015 "," EFKA-4046 "," EFKA-4047 "," EFKA-4055 "," EFKA-4050 "(manufactured by EFKA CHEMICALS) Examples of the colorant derivative include Solsperse 22000 (manufactured by Avicia). Of course, the pigment dispersant is not limited to these, and other dispersants can also be used.
Moreover, although the addition amount of a pigment dispersant changes with surface areas of a pigment, it is good to add 1-30% of mass ratio with respect to a pigment.

  The toner according to the present invention may further contain, for example, a release agent, inorganic fine particles, a charge control agent, a fluidity improver, a cleaning property improver, and the like depending on the purpose.

(Release agent)
Examples of the release agent include those shown below.
As a mold release agent, it can select suitably from well-known things according to the objective, For example, waxes, silicone oils, etc. are mentioned suitably.
Examples of the waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, silicone waxes, natural waxes, petroleum waxes, higher fatty acids and metal salts thereof, higher fatty acid amides, and various modified waxes thereof. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the low molecular weight polyolefin wax include low molecular weight polyethylene wax and low molecular weight polypropylene wax.
Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax.
Examples of the natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax.
Examples of the petroleum wax include paraffin wax and microcrystalline wax. Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and the like.

  Silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, polyether modified silicone oil, epoxy modified silicone oil, amino modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, carbinol modified. Silicone oil, methacrylic modified silicone oil, alkyl modified silicone oil, phenol modified silicone oil, fatty acid ester modified silicone oil, vinyl modified silicone oil, alkoxy modified silicone oil, heterogeneous functional group modified silicone oil, etc. One or more can be appropriately selected.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent (waxes), Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC Is particularly preferred.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. When the melting point exceeds 160 ° C., it may easily cause a cold offset when fixing at a low temperature. Paper wrapping may occur.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass parts is preferable and 3-30 mass parts is more preferable.
When the content exceeds 40 parts by mass, the low-temperature fixability may be hindered or the image quality may be deteriorated (the glossiness is too high).

In the present invention, 0 to 20 parts by weight, preferably 0 to 15 parts by weight, and more preferably 0 to 10 parts by weight of a release agent is added to 100 parts by weight of the ring-opening polymerizable monomer in the pigment dispersion. May be. By containing a release agent in the pigment dispersion, colored polymer particles containing the release agent can be obtained. In the dispersion polymerization in a supercritical fluid, the mechanism by which the release agent is included is not clear at present, but the following two mechanisms are conceivable.
One is considered to be that the mold release agent dissolves due to the plastic effect in heat and supercritical fluid and is taken in along with the dispersion polymerization, and the other is that the mold release agent dissolved in some supercritical fluids. It is considered that the polymer particles are taken in (injected) according to the distribution coefficient. From the TEM photograph of the obtained colored polymer particles, it can be confirmed that the release agent is included because lamella can be observed inside the particles.

  The release agent may be mixed and dispersed with a pigment or a ring-opening polymerizable monomer and contained in the ring-opening polymerizable monomer composition. In order to finely disperse the release agent, the release agent It is preferable to prepare a release agent dispersion prepared from the ring-opening polymerizable monomer and to mix and disperse the pigment and the ring-opening polymerizable monomer.

(Inorganic fine particles)
The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate , Zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide , Silicon nitride, and the like. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, as a specific surface area by BET method of the said inorganic fine particle, 20-500 m < ² > / g is preferable.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

(Charge control agent)
The charge control agent can be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is preferable. Dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus alone or its Examples thereof include a compound, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. There is no restriction | limiting in particular as said metal, According to the objective, it can select suitably, For example, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

The charge control agent may be a commercially available product. Examples of the commercially available product include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, cal Hexyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence or absence of the additive, and the like, and cannot be defined generally. 1-10 mass parts is preferable and 1-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charging characteristics of the toner may be deteriorated. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is increased. , And the electrostatic attraction force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

(Fluidity improver)
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents And silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.

(Cleaning improver)
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, for example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples include polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

  The shape, size, etc. of the toner is not particularly limited and can be appropriately selected according to the purpose. However, the following thermal characteristics, image density, average circularity, volume average particle diameter are as follows. It is preferable to have a ratio of volume average particle diameter to number average particle diameter (volume average particle diameter / number average particle diameter).

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, softening temperature (Ts), outflow start temperature (Tfb), 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 80-120 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.

There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 70-150 degreeC is more preferable. If the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.

<Developer>
The developer contains at least the toner of the present invention and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer, but when used for a high-speed printer that supports the recent improvement in information processing speed, In view of this, a two-component developer is preferable.

There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a copper-zinc (Cu—Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used individually by 1 type and may use 2 or more types together.

  The core material has a weight average particle diameter (D50) of preferably 10 to 200 μm, more preferably 40 to 100 μm. If the weight average particle size (D50) is less than 10 μm, the fine particle system is increased in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering, and if it exceeds 200 μm, the specific surface area decreases. Toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. Examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, and polyesters. Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and fluoride Examples include vinyl copolymers, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers (triple fluoride (multiple) copolymers), silicone resins, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, silicone resins are particularly preferable.

  There is no restriction | limiting in particular as said silicone resin, According to the objective from the silicone resin generally known, it can select suitably according to the objective, for example, straight silicone resin which consists only of organosiloxane bonds; alkyd resin, polyester Examples thereof include silicone resins modified with resins, epoxy resins, acrylic resins, urethane resins, and the like.

Examples of commercially available silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone. As modified silicone resins, KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy modified) manufactured by Toray Dow Corning Silicone Co., Ltd. ), SR2110 (alkyd modified), and the like.
It is possible to use a silicone resin alone, but it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

  The resin layer may contain conductive powder, if necessary, and examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

  For example, the resin layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core by a known coating method, drying, and baking. Can be formed. Examples of the application method include an immersion method, a spray method, and a brush coating method.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace Etc., a method using a microwave, and the like.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount of the resin layer is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thicker. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable mixing ratio of the toner and the carrier is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Image forming device)
Here, FIG. 3 shows a schematic configuration diagram of a main part of an example of the image forming apparatus (copier) used in the embodiment.
1 is an electrostatic latent image carrier (photosensitive drum), 2 is a charging device, 3 is an exposure device, 4 is a developing device, 5 is a transfer device, 6 is a fixing device, 7 is a cleaning member, 43 is a developing sleeve, S is a sheet (transfer paper or the like).

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

<Measurement of molecular weight of polymer>
The measurement was performed by GPC (gel permeation chromatography) under the following conditions.
-Equipment: GPC-8020 (manufactured by Tosoh Corporation)
Column: TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min 1 mL of a sample having a concentration of 0.5% by mass is injected, and the number of toners is calculated using a molecular weight calibration curve created from a monodisperse polystyrene standard sample from the molecular weight distribution of the polymer measured under the above conditions. Average molecular weight Mn and mass average molecular weight Mw were calculated. The molecular weight distribution is a value obtained by dividing Mw by Mn.

<Polymer conversion rate of monomer (mol%) = 100-unreacted monomer amount (mol%)>
In the case of polylactic acid, the amount of unreacted monomer (mol%) is determined by using a nuclear magnetic resonance apparatus JNM-AL300 manufactured by JEOL Ltd. in deuterated chloroform. .20 ppm) is calculated as a lactide-derived quadruple peak area ratio (4.98 to 5.05 ppm), which is multiplied by 100.
In the case of polycaprolactone, the unreacted monomer amount (mol%) was determined by using a nuclear magnetic resonance apparatus JNM-AL300 manufactured by JEOL Ltd. in deuterated chloroform, and the triple line peak area ratio derived from polycaprolactone (4.04-4. It is calculated as a triplet peak area ratio (4.22 to 4.25 ppm) derived from caprolactone with respect to (08 ppm), and is multiplied by 100.
In the case of polycarbonate, the amount of unreacted monomer (mol%) was determined by using a nuclear magnetic resonance apparatus JNM-AL300 manufactured by JEOL Ltd. in deuterated chloroform, and a quadruple peak area ratio (4.22 to 4.25 ppm derived from polycarbonate). ) Is calculated as an ethylene carbonate-derived singlet peak area ratio (4.54 ppm), which is multiplied by 100.

<Toner surface hydrophobicity>
In a 20 ml vial, 15 ml of ion exchange water was added, and 0.1 g of toner was added and checked for 10 minutes. Then, after leaving for one day, the following judgment was made according to the state in the vial bottle.
○: The toner is completely separated from the water and floats on the water layer.
Δ: Toner and water are mixed, but the grain boundary of the toner is clearly understood.
X: Toner and water are completely mixed.

<Synthesis Example 1>
-Synthesis of Surfactant 2-
1250 parts by mass of 1H, 1H-perfluorooctyl acrylate (manufactured by Amax Co.), 62.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., V-65) The reaction cell (50% by volume of the pressure vessel cell) is filled, carbon dioxide is selected as a supercritical fluid, this carbon dioxide is supplied to the reaction cell by a supply cylinder, and 15 MPa, 85 by a pressure pump and a temperature controller. The reaction was carried out for 24 hours while adjusting the temperature.
Next, the temperature was lowered to 0 ° C., and the pressure was lowered to normal pressure using a back pressure valve, to obtain a surfactant 2 represented by the following structural formula. Its number average molecular weight (Mn) was 2500.

但し、上記式においてｑは繰り返し単位を表す整数である。 [Surfactant 2]

In the above formula, q is an integer representing a repeating unit.

<Synthesis Example 2>
-Synthesis of surfactant 3-
In a 6 mL vial, polyacrylic acid 5,000 (Wako Pure Chemical: 36.1 parts by mass), chloroform (Wako Pure Chemical: 1480 parts by mass), 1,1′-carbonylbis-1H-imidazole (128 parts by mass) And stirred at room temperature for 10 minutes.
Then, polyethylene glycol (Wako Pure Chemical Industries, molecular weight 200: 500 parts by mass) was added and stirred at room temperature for 12 hours.
Next, chloroform was added and washed with water.
Subsequently, after drying with anhydrous sodium sulfate, filtration and further concentration under reduced pressure, a surfactant 3 represented by the following structural formula was obtained (yield: 73 mass%). Its number average molecular weight (Mn) was 5200.

但し、上記式においてｒ及びｐは繰り返し単位を表す整数である。 [Surfactant 3]

In the above formula, r and p are integers representing repeating units.

<Synthesis Example 3>
-Synthesis of surfactant 4-
In a 50 mL eggplant-shaped flask, side chain carboxy-modified silicone oil (Shin-Etsu Silicone: KF-8012, molecular weight 4500: 12 parts by mass), chloroform (Wako Pure Chemicals, 33.3 parts by mass), 1,1′-carbonylbis-1H -Imidazole and polyethylene glycol (Wako Pure Chemicals, molecular weight 200: 1.3 parts by mass) were added and stirred at room temperature for 12 hours.
Next, a saturated aqueous sodium hydrogen carbonate solution was added, and the precipitated sodium stearate was filtered through a Kiriyama funnel, followed by washing with a saturated aqueous sodium hydrogen carbonate solution.
Subsequently, after drying with anhydrous sodium sulfate, the mixture was filtered through silica gel and further concentrated under reduced pressure to obtain a surfactant 4 represented by the following structural formula (yield: 91% by mass). Its number average molecular weight (Mn) was 4,700.

但し、上記構造式においてｍ、ｎ及びｐは繰り返し単位を表す整数である。またＲは炭素数１〜４の低級アルキル基を表す。 [Surfactant 4]

However, m, n, and p in the above structural formula are integers representing repeating units. R represents a lower alkyl group having 1 to 4 carbon atoms.

<Synthesis Example 4>
-Synthesis of surfactant 9-
Side chain amino-modified both-end methoxy-modified silicone oil (Shin-Etsu Silicone: KF-857, molecular weight 790: 7.9 parts by mass), dichloromethane (Tokyo Kasei: 66.6 parts by mass), phenyl isocyanate (Kanto Chemical) : 3.6 parts by mass) and stirred at room temperature for 24 hours. Hexane was then added and washed with distilled water. After drying over anhydrous sodium sulfate, cotton wire filtration and silica gel filtration were performed, and the solvent was distilled off under reduced pressure to obtain surfactant 9 (yield: 80%).

<Synthesis Example 5>
-Synthesis of surfactant 10-
Surfactant 10 was obtained by the same procedure as in Synthesis Example 8 except that it was changed to phenyl isothiocyanate (Wako Pure Chemical: 4.0) in Synthesis Example 8.

<Preparation of ring-opening polymerizable monomer composition 1>
C. I. Pigment Yellow PY180 (50 parts by mass), L-lactide (882.4 parts by mass), 4-dimethylaminopyridine (48.9 parts by mass), Surfactant 1 (49.7 parts by mass), silicone wax (Toray Dow) Corning, trade name: AMS-C30, 50 parts by mass), 3 mmφ YTZ zirconia beads (10000 parts by mass) are placed in a container, and uniformly dispersed for 4 hours in a paint shaker (Seiwa Giken Co., Ltd.). Ring-opening polymerization Monomer composition 1 was prepared.

<Example 1>
In a pressure vessel, ring-opening polymerizable monomer composition 1 (1080 parts by mass), L-lactide (882.4 parts by mass), 4-dimethylaminopyridine (48.9 parts by mass), surfactant 1 (49.7 parts by mass). And a microtube containing dehydrated ethanol (9.2 parts by mass) was added and warmed to 60 ° C., then charged with supercritical carbon dioxide (60 ° C., 30 MPa), and reacted at 60 ° C. for 2 hours. .
Next, using a pressurization pump and a back pressure valve, the flow rate on the outlet side of the back pressure valve is adjusted to 5.0 L / min, and supercritical carbon dioxide is flown for 30 minutes to remove the organic catalyst and residual monomer. The temperature was gradually returned to normal temperature and normal pressure, and after 3 hours, the colored polymer particles 1 inside the container were taken out.

  In this way, 0.7 parts by mass of hydrophobic silica and 0.3 parts by mass of hydrophobized titanium oxide are added to 100 parts by mass of the colored polymer particles 1 thus obtained, and the peripheral speed is 8 m / s using a Henschel mixer. For 5 minutes. The mixed powder was passed through a mesh having an opening of 100 μm, and coarse powder was removed to obtain toner 1. Next, the container 1 rolls and stirs the toner 1, 5% by mass subjected to the external additive treatment, and 95% by mass of the copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with the silicone resin. A two-component developer 1 was prepared by uniformly mixing and charging using a tumbler mixer.

<Examples 2 to 24>
Example 1 except that the catalyst species used, the type / amount of the surfactant, the monomer species, and the reaction conditions are the combinations shown in the columns of Examples 2 to 24 in Table 1-1 to Table 1-3. According to the procedure, toners 2 to 24 were obtained, and then two-component developers 2 to 24 were obtained.
In addition, the structure of surfactant 5-10 is shown by the following structural formula.

[Surfactant 5]

[Surfactant 6]

[Surfactant 7]

[Surfactant 8]

[Surfactant 9]

[Surfactant 10]

  Tables 1-1 to 1-3 show the physical property values (Mn, Mw / Mn, polymer conversion rate, surface hydrophobicity) obtained by the above-described methods for these toners.

-Production of resin (b)-
Into an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen insertion tube, the raw materials shown in polyester diol (b11) in Table 2 and 2 parts of tin 2-ethylhexylate were placed at 160 ° C. at atmospheric pressure, The ring-opening polymerization was performed for a period of time, and the reaction was further performed at normal pressure and 130 ° C. The taken-out resin was cooled to room temperature, and then pulverized into polyester diols (b11) -1 and (b11) -2 containing polyhydroxycarboxylic acid skeletons.
Polyester diols (b12) -1 and (b12) -2 obtained by dehydrating and condensing the raw materials shown in the polyester diol (b12) of Table 2, and the previously obtained polyester diol (b11) -1 (b11)- Each of 2 is dissolved in methyl ethyl ketone, followed by addition of IPDI as an extender, an extension reaction is performed at 50 ° C. for 6 hours, and the solvent is distilled off to obtain [Resin b-1] and [Resin b-2]. Obtained.

  L-lactide, D-lactide, ε-caprolactone, and tin octylate are added to a four-necked flask in the number of parts shown in Table 3, and heated and melted at 120 ° C. for 20 minutes in a nitrogen atmosphere. The mixture was added in the indicated number and melted by heating at 190 ° C. for 3 hours. Thereafter, residual lactide and caprolactone were distilled off under reduced pressure to obtain [Resin b-3] and [Resin b-4].

-Synthesis of polyester prepolymer-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 720 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 90 parts by mass of bisphenol A propylene oxide 2-mole adduct, 290 parts by mass of terephthalic acid, anhydrous 25 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and then reacted for 7 hours under reduced pressure of 10 to 15 mmHg to synthesize an intermediate polyester resin.
The obtained intermediate polyester resin has a number average molecular weight (Mn) of 2,500, a mass average molecular weight (Mw) of 10,700, a peak molecular weight of 3,400, a glass transition temperature (Tg) of 57 ° C., an acid value. Of 0.4 mgKOH / g and hydroxyl value of 49 mgKOH / g.

  Next, 400 parts by mass of the intermediate polyester resin, 95 parts by mass of isophorone diisocyanate, and 580 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 100 ° C. for 8 hours. By reacting, a [polyester prepolymer] was synthesized. The obtained polyester prepolymer had a free isocyanate content of 1.42% by mass.

-Production of graft polymer-
In a reaction vessel equipped with a stir bar and a thermometer, 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) are sufficiently dissolved. After substitution with nitrogen, 755 parts by mass of styrene, 100 parts by mass of acrylonitrile, 45 parts by mass of butyl acrylate, 21 parts by mass of acrylic acid, 36 parts by mass of di-t-butylperoxyhexahydroterephthalate, and 100 parts by mass of xylene Was added dropwise at 170 ° C. for 3 hours for polymerization, and further maintained at this temperature for 0.5 hour. Subsequently, the solvent was removed to synthesize a graft polymer. The obtained graft polymer has a number average molecular weight: 3,300, a mass average molecular weight: 18,000, a glass transition point: 65.0 ° C., and a SP value of vinyl resin: 11.0 (cal / cm ³ ) ^{1 / 2} .

-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The obtained ketimine compound had an amine value of 423 mgKOH / g.

-Preparation of master batch-
1,000 parts by weight of water, 530 parts by weight of carbon black (Printex 35, manufactured by Degussa) having a DBP oil absorption of 42 ml / 100 g and a pH of 9.5, and 1200 parts by weight of [resin b-1] were added to a Henschel mixer. (Mitsui Mining Co., Ltd.) was used for mixing. The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch 1].
[Masterbatch 2] to [Masterbatch 4] were produced in the same manner except that [Resin b-1] was changed to [Resin b-2] to [Resin b-4].

-Production of resin (a)-
A mixture consisting of 1,578 g of terephthalic acid, 83 g of isophthalic acid, 374 g of ethylene glycol and 730 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 2.5 hours to carry out an esterification reaction. Next, 0.262 g of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under this condition, the polycondensation reaction was continued. After 1.5 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 260 ° C., 50 g of isophthalic acid and 38 g of trimellitic anhydride were added, The mixture was stirred at 255 ° C. for 30 minutes and discharged into a sheet. And this was fully cooled to room temperature, Then, it grind | pulverized with the crusher, The fraction of 1-6 mm of openings was obtained as a polyester resin (a-1) using the sieve. Table 4 shows the analysis results of the polyester resin a-1.

-Production of polyester resin (a-2) and polyester resin (a-3)-
Various resins (a-2) and resins (a-3) were produced in the same manner as in the resin (a-1). The analysis results for each resin are shown in Table 4.

-Production of fine particle dispersion (w)-
Polyester resin (a-1) 200 g, ethylene glycol-n-butyl ether 35 g, polyvinyl alcohol (Unitika Ltd. “Unitikapoval” 050G) 0.5% by mass aqueous solution (hereinafter referred to as PVA-1) in a 2 L glass container with a jacket ) 459 g and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 times equivalent of the total amount of carboxyl groups contained in the polyester resin, and this is an open system desktop homodisper (special When the mixture was stirred at 6,000 rpm using Kika Kogyo Co., Ltd. (TK Robotics), no precipitation of resin particles was observed at the bottom of the container, confirming that it was in a completely floating state. Therefore, this state was maintained, and hot water was passed through the jacket after 10 minutes for heating. When the temperature in the container reached 68 ° C., the stirring was set at 7,000 rpm, the temperature in the container was kept at 68 to 70 ° C., and the mixture was further stirred for 20 minutes to obtain a milky white uniform aqueous dispersion. Then, cold water was poured into the jacket, cooled to room temperature while stirring at 3500 rpm, and filtered using a stainless steel filter (635 mesh, plain weave). As a result, almost no resin particles remained on the filter. Table 5 shows the analysis results of the obtained filtrate fine particle dispersion (w-1).

-Production of fine particle dispersion (w-2) and fine particle dispersion (w-3)-
In the same manner as the fine particle dispersion (w-1), an aqueous solution was attempted using various raw materials. Table 5 shows the composition of the obtained fine particle dispersion.

-Production of fine particle dispersion (w-4)-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 6 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid monobutyl methacrylate-alkylallylsulfosuccinic acid sodium salt) [fine particle dispersion (W-4)] was obtained. The volume average particle size of the fine particle dispersion (W-4) measured by ELS-800 was 0.08 μm. A part of the fine particle dispersion (W-4) was dried to isolate the resin component, and the glass transition temperature measured by a flow tester measurement was 74 ° C.

-Preparation of aqueous medium-
300 parts by weight of ion-exchanged water, 300 parts by weight of the fine particle dispersion (W-1), and 0.2 parts by weight of sodium dodecylbenzenesulfonate were mixed and stirred to dissolve uniformly to prepare [Aqueous Medium Phase 1].

-Preparation of resin solution-
Polyester resin (the above [resin b-1]-[resin b-4]) and [polyester prepolymer] are added to the reaction vessel in the number of parts shown in Table 6, and 80 parts by mass of ethyl acetate is further added and stirred. Resin solutions 1 to 4 were prepared.

-Preparation of emulsion-
Next, 5 parts by weight of carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)) and graft polymer 0.75 mass were added to resin solution 1 to resin solution 4. And 5 parts by mass of [Masterbatch 1], using a bead mill Ultra Visco Mill (manufactured by Imex), liquid feed speed 1 kg / hour, disk peripheral speed 6 m / sec, particle size 0.5 mm zirconia Three passes were carried out under the condition that 80% by volume of beads were filled. Further, 2.5 parts by mass of a ketimine compound was added and dissolved to obtain a toner material liquid.

  Next, 150 parts by mass of [Aqueous medium phase 1] is put in a container, and 100 parts by mass of the toner material solution is added while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was added and mixed for 10 minutes to obtain an emulsified slurry. Further, 100 parts by mass of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.

Next, 100 parts by mass of the dispersed slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed at 12,000 rpm for 10 minutes using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. After adding 20 parts by mass of 10% by mass hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK homomixer, the fluorine-based quaternary ammonium salt compound, F-310 (Neos). Was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part by mass with respect to 100 parts by mass of the solid content of the toner, stirred for 10 minutes, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake. The obtained filter cake was dried at 40 ° C. for 36 hours using a circulating dryer, and sieved with a mesh having a mesh opening of 75 μm to prepare toner base particles 25.
Similarly, toner base particles 26 to 28 were produced.

[Comparative Example 1] to [Comparative Example 4]
-Preparation of toner-
100 parts by mass of the obtained toner base particles 25 to 28 and 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After 5 cycles of mixing at a peripheral speed of 30 m / sec for 30 seconds and resting for 1 minute, sieved with a mesh having an opening of 35 μm, toners 25 to 28 of Comparative Examples 1 to 4 were produced.
Table 8 shows the physical property values of the obtained toner.

-Production of developer-
Developers of Comparative Examples 1 to 4 were prepared in the same procedure as in Example 1 using toners 25 to 28.
Next, using the developer, fixability, wet heat resistance and environmental stability were evaluated as follows.
The results are shown in Table 9.

<Fixability>
Plain paper and cardboard are used by changing the temperature of the fixing belt using an apparatus in which the fixing unit of an electrophotographic copying machine (MF-200, manufactured by Ricoh) is using a Teflon (registered trademark) roller as a fixing roller. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on the transfer paper type 6200 (manufactured by Ricoh Company) and copy printing paper <135> (manufactured by NBS Ricoh Company). At this time, the upper limit temperature at which hot offset does not occur on plain paper was taken as the fixing upper limit temperature. Further, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with a pad was 70% or more was defined as the minimum fixing temperature. Evaluation of AC is a pass standard.

[Evaluation criteria for maximum fixing temperature]
A: 190 ° C or higher B: 180 ° C or higher and lower than 190 ° C C: 170 ° C or higher and lower than 180 ° C D: Less than 170 ° C

[Evaluation criteria for minimum fixing temperature]
A: Less than 135 ° C B: 135 ° C or more and less than 145 ° C C: 145 ° C or more and less than 155 ° C D: 155 ° C or more

<Moisture and heat resistance>
4 g of toner was placed in an open cylindrical container having a diameter of 5 cm and a height of 2 cm, and left for 72 hours in an environment of a temperature of 45 ° C. and a relative humidity of 65%. After leaving, the container containing the toner was shaken lightly, and the presence or absence of toner aggregation was visually observed, and the storage stability was evaluated according to the following evaluation criteria. Evaluation of AC is a pass standard.

〔Evaluation criteria〕
A: No toner aggregation observed B: 1-2 toner aggregation particles observed C: 3-5 toner aggregation particles observed D: 6 toner aggregation particles observed Observed above

<Environmental stability>
The developer obtained was stirred with a ball mill for 5 minutes in an environment with an air temperature of 23 ° C. and a humidity of 50% RH (M / M environment), and 1.0 g of the developer was sampled, and a blow-off charge measuring device (Kyocera Chemical) TB-200) was used, and the measured value after nitrogen blowing for 1 minute was used as the charge amount. Each developer is measured under two conditions: an ambient temperature of 40 ° C. and a humidity of 90% RH (H / H environment), and an ambient temperature of 10 ° C. and a humidity of 30% RH (L / L environment). The charge amount of was evaluated. The environmental fluctuation rate was calculated from the following formula. It can be said that the lower the environmental fluctuation rate, the more stable the charging property. Evaluation of AC is a pass standard.

〔Evaluation criteria〕
A: Environmental change rate is less than 10% B: Environmental change rate is 10% or more and less than 30% C: Environmental change rate is 30% or more and less than 50% D: Environmental change rate is 50% or more

  The toner produced by this production method has both a fixing property and a heat-and-moisture resistance because the resin surface is hydrophobic, so that there is little variation in the environment of the charge amount, and since the molecular weight distribution of the resin is small.

1 Electrostatic latent image carrier (photosensitive drum)
2 Charging device 3 Exposure device 4 Developing device 5 Transfer device 6 Fixing device 7 Cleaning member 43 Developing sleeve S Sheet (transfer paper, etc.)

JP 2009-167409 A JP 2009-132878 A Japanese Patent Laid-Open No. 04-179967 JP 2008-262179 A Japanese Patent No. 2597452 JP 2006-091278 A JP 2006-285150 A

Claims (12)

  1. A toner obtained by granulating a ring-opening polymerizable monomer using a catalyst in the presence of a surfactant and a colorant in a compressive fluid.   The toner according to claim 1, wherein the catalyst is an organic catalyst.   The toner according to claim 2, wherein the organic catalyst is a basic nucleophilic nitrogen compound.   The toner according to claim 2, wherein the organic catalyst is a cyclic compound containing a nitrogen atom.   1 wherein the organic catalyst is selected from a cyclic amine, a cyclic diamine, a cyclic diamine compound having an amidine skeleton, a cyclic triamine compound having a guanidine skeleton, a heterocyclic aromatic organic compound containing a nitrogen atom, and an N-heterocyclic carbene. The toner according to claim 2, wherein the toner is a seed.   The organic catalyst is 1,4-diazabicyclo- [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5,7- Triazabicyclo [4.4.0] dec-5-ene (TBD), diphenylguanidine (DPG), N, N-dimethyl-4-aminopyridine (DMAP), 4-pyrrolidinopyridine (PPY), 1, The toner according to claim 5, wherein the toner is any one of 3-di-tert-butylimidazol-2-ylidene (ITBU).   The toner according to claim 1, wherein the colorant is a pigment.   The toner according to claim 1, wherein the ring-opening polymerizable monomer is L- or D-lactic acid lactide.   The toner according to claim 1, wherein the surfactant has affinity for both the compressive fluid and the ring-opening polymerizable monomer.   The toner according to claim 1, wherein the surfactant has any one of a perfluoroalkyl group, a polydimethylsiloxane group, and a polyacrylate group. The toner according to any one of claims 1 to 10, the molecular weight distribution of the toner molecular weight distribution (Mw / Mn), characterized in that more than 1.5.
However, Mw represents a mass average molecular weight and Mn represents a number average molecular weight. A method for producing a toner, comprising granulating a compressive fluid while polymerizing a ring-opening polymerizable monomer using a catalyst in the presence of a surfactant and a colorant.

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